Herbicidal substituted azines

ABSTRACT

Herbicidal substituted azines of the formula ##STR1## in which m represents the numbers 0, 1, 2 or 3, 
     A represents nitrogen or a C-X group where X represents hydrogen or halogen, 
     Q represents oxygen or sulphur, 
     R 1  and R 2  are identical or different and represent hydrogen, halogen, alkyl, halogenoalkyl, alkoxy-alkyl, alkoxy, halogenoalkoxy, alkylthio, alkylamino or dialkylamino, 
     R 3  represents amino, hydroxyl, halogen, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylamino, dialkylamino, alkylcarbonylamino, alkoxycarbonyl-amino or alkylsulphonylamino, 
     R 4  represents hydrogen or alkyl and 
     Z represents N--R 5  or ##STR2##

The invention relates to new substituted azines, to a process and to newintermediates for their preparation, and to their use as herbicides.

A series of substituted azines having herbicidal properties has alreadybeen disclosed (compare JP-A 54117486 - cit. in Chem. Abstracts 93,150268c; EP-A 223,406; EP-A 249,708; JP-A 63258467 - cit. in Chem.Abstracts 110, 130532a; JP-A 63258463 - cit. in Chem. Abstracts 110,192853q; EP-A 287,079; EP-A 374,839). However, compounds from thepublications mentioned have not gained considerable importance to date.

The new substituted azines of the general formula (I) have now beenfound, ##STR3## in which m represents the numbers 0, 1, 2 or 3,

A represents nitrogen or a C-X group where X represents hydrogen orhalogen,

Q represents oxygen or sulphur,

R¹ and R² are identical or different and represent hydrogen, halogen,alkyl, halogenoalkyl, alkoxyalkyl, alkoxy, halogenoalkoxy, alkylthio,alkylamino or dialkylamino,

R³ represents amino, hydroxyl, halogen, alkyl, halogenoalkyl, alkoxy,halogenoalkoxy, alkylamino, dialkylamino, alkylcarbonylamino,alkoxycarbonylamino or alkylsulphonylamino,

R⁴ represents hydrogen or alkyl and

Z represents one of the groups below:

N-R⁵ or ##STR4## where R⁵ represents hydrogen, amino, or in each caseoptionally substituted alkyl, alkenyl, alkynyl, aralkyl, aryl,alkoxycarbonyloxy,arylaminocarbonyloxy,carboxyalkoxy,alkoxycarbonylalkoxy, alkylamino,dialkylamino, aralkylamino, arylamino, N-alkyl-N-arylamino,alkylcarbonylamino, arylcarbonylamino, heteroarylamino,heteroarylcarbonylamino, alkoxycarbonylamino, alkylsulphonylamino orarylsulphonylamino,

R⁶ represents hydrogen, halogen, cyano, carboxyl, alkoxycarbonyl,alkylcarbonylamino or dialkoxyphosphoryl and

R⁷ represents formyl, cyano, carboxyl, hydroxymethyl, carbamoyl, or ineach case optionally substituted alkoxycarbonyl, cycloalkoxycarbonyl,aralkoxycarbonyl, aryloxycarbonyl, heterocyclylalkoxycarbonyl,alkylthiocarbonyl, aralkylthiocarbonyl, arylthiocarbonyl,alkylaminocarbonyl, cycloalkylaminocarbonyl, aralkylaminocarbonyl,arylaminocarbonyl, dialkylaminocarbonyl, alkylhydrazinocarbonyl,arylhydrazinocarbonyl,pyrrolidinylcarbonyl,piperidinylcarbonyl,morpholinylcarbonyl,piperazinylcarbonyl, phthalimidoxycarbonyl, or represents the group##STR5## in which A, Q, R¹ and R² have the meanings given above, ortogether with R⁶ represents the group --CO--O--(CH₂)_(n) -- where nrepresents the numbers 1 to 4.

The new substituted azines of the general formula (I) are obtained whencorresponding carbonyl compounds of the general formula (II) ##STR6## inwhich m, A, Q, R¹, R², R³ and R⁴ have the meaningsgiven above,

are reacted with amino or methylene compounds of the general formula(II)

    H.sub.2 Z                                                  (III)

in which

Z has the meaning given above,

if appropriate in the presence of a reaction auxiliary and ifappropriate in the presence of a diluent, and, if appropriate, theproducts obtained in this process are subsequently converted into otherderivatives according to the definition of the compounds of the formula(I) using customary methods.

The new substituted azines of the general formula (I) are distinguishedby a powerful herbicidal action.

The invention preferably relates to compounds of the formula (I) inwhich

m represents the numbers 0, 1, or 2,

A represents nitrogen or a C-X group where X represents hydrogen orhalogen,

Q represents oxygen or sulphur,

R¹ and R² are identical or different and represent hydrogen, halogen, C₁-C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -halogeno alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylaminoor di-(C₁ -C₂ -alkyl)-amino,

R³ represents amino, hydroxyl, halogen, C₁ -C₄ -alkyl, C₁ -C₄-halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄-alkylamino, di-(C₁ -C₂ -alkyl)-amino, C₁ -C₄ -alkyl-carbonylamino,C₁-C₄ -alkoxy-carbonylamino or C₁ -C₄ -alkylsulphonylamino,

R⁴ represents hydrogen or C₁ -C₄ -alkyl and

Z represents one of the groups below:

N-R⁵ or ##STR7## where R⁵ represents hydrogen, amino or represents C₁-C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, carboxy-C₁ -C₂ -alkoxy, C₁-C₆ -alkoxycarbonyloxy, C₁ -C₄ -alkoxycarbonyl-C₁ -C₂ -alkoxy, C₁ -C₆-alkylamino, di-(C₁ -C₂ -alkyl)-amino, C₁ -C₆ -alkyl-carbonylamino, C₁-C₆ -alkoxy-carbonylamino or C₁ -C₆ -alkyl-sulphonylamino, each of whichis optionally substituted by halogen, or represents phenyl, phenyl-C₁-C₄ -alkyl, phenylaminocarbonyloxy, phenylamino, phenyl-C₁ -C₄-alkylamino, N-(C₁ -C₄ -alkyl)-phenylamino, pyridylamino,pyrimidylamino, pyridylcarbonylamino, phenylcarbonylamino,furylcarbonylamino, thienylcarbonylamino or phenylsulphonylamino, eachof which is optionally substituted by nitro, hydroxyl, amino, cyano,carboxyl, halogen, C₁ -C₄ -alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₄ -alkoxy,C₁ -C₂ -halogenoalkoxy, C₁ -C₄ -alkylthio, C C₁ -C₄ -alkoxycarbonyland/or di-(C₁ -C₂ -alkyl)-amino,

R⁶ represents hydrogen, halogen, cyano, carboxyl, C₁ -C₆-alkoxy-carbonyl, C₁ -C₆ -alkylcarbonylamino or di-(C₁ -C₄-alkoxy)-phosphoryl, and

R⁷ represents formyl, cyano, carboxyl, hydroxymethyl or carbamoyl, orrepresents C₁ -C₆ -alkoxy-carbonyl, C₅ -C₆ -cycloalkyloxy-carbonyl, C₁-C₆ -alkylthiocarbonyl, C₁ -C₆ -alkylamino-carbonyl or C₅ -C₆-cycloalkylamino-carbonyl, each of which is optionally substituted byhalogen, carboxyl or C₁ -C₄ -alkoxycarbonyl, or represents di-(C₁ -C₂-alkyl)-aminocarbonyl, or C₁ -C₄ -alkylamino-carbonyl-C₁ -C₄-alkoxy-carbonyl, or di-(C₁ -C₂ -alkyl)-aminocarbonyl-C₁ -C₄-alkoxy-carbonyl, or phenylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, orN-methylphenylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, or representspyrrolidinylcarbonyl, piperidinylcarbonyl, morpholinylcarbonyl orpiperazinylcarbonyl, each of which is optionally substituted by methyland/or ethyl, or represents phenoxycarbonyl, phenyl-C₁ -C₄-alkoxycarbonyl, furylmethoxycarbonyl, thienylmethoxycarbonyl,phenylthiocarbonyl, phenyl-C₁ -C₄ -alkylthio-carbonyl,phenylaminocarbonyl, phenyl-C₁ -C₄ -alkylaminocarbonyl, N-(C₁ -C₄-alkyl)-phenylamino-carbonyl or phenylhydrazinocarbonyl, each of whichis optionally substituted by nitro, amino, cyano, carboxyl, halogen, C₁-C₄ -alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₂-halogenoalkoxy, C₁ -C₄ -alkylthio, C.sub. 1 -C₂ -halogenoalkylthio, C₁-C₄ -alkoxycarbonyl and/or di-(C₁ -C₂ -alkyl)-amino, or representsphthalimidoxycarbonyl, or represents the group ##STR8## in which A, Q,R¹ and R² have the meanings given above as being preferred, or togetherwith R⁶ represents the group --CO--O--(CH₂)_(n) -- where n representsthe numbers 2 or 3.

The aliphatic hydrocarbon radicals listed in the definition of thecompounds according to the invention (for example alkyl, alkenyl,alkynyl) are in each case straight-chain or branched, also incombination with heteroatoms (for example in alkoxy, alkylthio,alkylamino).

Halogen in each case generally represents fluorine, chlorine, bromine oriodine, preferably fluorine, chlorine or bromine, in particular fluorineor chlorine.

In particular, the invention relates to compounds of the formula (I), inwhich

m represents the numbers 0, 1, or 2,

A represents nitrogen or a CH group,

Q represents oxygen,

R¹ represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl,methoxymethyl, methoxy, ethoxy, difluoromethoxy, methylthio,methylamino, ethylamino or dimethylamino,

R² represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl,methoxy, ethoxy, difluoromethoxy, methylthio, methylamino, ethylamino ordimethylamino,

R³ represents amino, hydroxyl, fluorine, chlorine, bromine, methyl,ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy,methylamino, dimethylamino, acetylamino, methoxycarbonylamino ormethylsulphonylamino,

R⁴ represents hydrogen or methyl and

Z represents one of the groups below:

N-R⁵ or ##STR9## where R⁵ represents hydrogen, amino, or methyl, ethyl,propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, allyl,propargyl, carboxymethoxy, carboxyethoxy, methoxycarbonyloxy,ethoxycarbonyloxy, propoxycarbonyloxy, butoxycarbonyloxy,methoxycarbonylmethoxy, ethoxycarbonylmethoxy, methoxycarbonylethoxy,ethoxycarbonylethoxy, methylamino, ethylamino, propylamino,isopropylamino, butylamino, isobutylamino, secbutylamino,tert-butylamino, dimethylamino, acetylamino, propionylamino,methoxycarbonylamino, ethoxycarbonylamino, methylsulphonylamino orethylsulphonylamino or represents phenyl, benzyl,phenylaminocarbonyloxy, phenylamino, benzylamino, N-methyl-phenylamino,pyridylamino, pyrimidylamino, pyridylcarbonylamino, phenylcarbonylamino,furylcarbonylamino, thienylcarbonylamino or phenylsulphonylamino, eachof which is optionally substituted by nitro, hydroxyl, cyano, fluorine,chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy,methylthio or trifluoromethylthio,

R⁶ represents hydrogen, fluorine, chlorine, cyano, carboxyl, C₁ -C₄-alkoxy-carbonyl, C₁ -C₄ -alkylcarbonylamino, dimethoxyphosphoryl ordiethoxyphosphoryl, and

R⁷ represents formyl, cyano, carboxyl, hydroxymethyl or carbamoyl, orrepresents C₁ -C₄ -alkoxy-carbonyl, C₅ -C₆ -cycloalkyloxy-carbonyl, C₁-C₄ -alkylthiocarbonyl, C₁ -C₄ -alkylamino-carbonyl or C₅ -C₆-cycloalkylamino-carbonyl, each of which is optionally substituted byfluorine, chlorine, carboxyl or C₁ -C₄ -alkoxy-carbonyl, or representsdimethylaminocarbonyl, or C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄-alkoxy-carbonyl, or dimethylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, orN-methylphenylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, or representspyrrolidinyl-carbonyl, piperidinylcarbonyl, morpholinyl-carbonyl orpiperazinylcarbonyl, each of which is optionally substituted by methyland/or ethyl, or represents phenoxycarbonyl, benzyloxycarbonyl,phenylthiocarbonyl, benzylthiocarbonyl, phenylaminocarbonyl,benzylaminocarbonyl, N-methyl-phenylaminocarbonyl orphenylhydrazinocarbonyl, each of which is optionally substituted bynitro, cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl,methoxy, trifluoromethoxy, methylthio or trifluoromethylthio, orrepresents phthalimidoxycarbonyl, or represents the group ##STR10## inwhich A, Q, R¹ and R² have the meanings given above as beingparticularly preferred, or together with R⁶ represents the group--CO--O--CH₂ CH₂ --.

Very particularly preferred compounds of the formula (I) are those inwhich

m represents the numbers 0, 1 or 2,

A represents a CH group,

Q represents oxygen,

R¹ represents methoxy,

R² represents methoxy,

R³ represents fluorine, chlorine or methyl,

R⁴ represents hydrogen and

Z has the meaning given above as being particularly preferred.

If, for example, 2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)benzaldehyde andacetohydrazide are used as starting substances in the process for thepreparation of the compounds of the formula (I) according to theinvention, the course of the reaction can be outlined by the followingequation: ##STR11## Formula (II) provides a general definition of thecarbonyl compounds to be used as starting substances in the process forthe preparation of compounds of the formula (I) according to theinvention.

In formula (II), A, Q, R¹, R², R³ and R⁴ preferably, or in particular,have the meanings which have already been given above in connection withthe description of the compounds of the formula (I) according to theinvention as being preferred, or as particularly preferred, for A, Q,R¹, R², R³ and R⁴.

Examples of the starting substances of the formula (II) which may bementioned are:

2-(4,6-dimethyl-pyrimidin-2-yl-oxy)-,

2-(4-methoxy-6-methyl-pyrimidin-2-yl-oxy)-,

2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-,

2-(4-methoxy-6-trifluoromethyl-pyrimidin-2-yl-oxy)-,

2-(4,6-dimethyl-s-triazin-2-yl-oxy)-,

2-(4-methoxy-6-methyl-s-triazin-2-yl-oxy)- and

2-(4,6-dimethoxy-s-triazin-2-yl-oxy)-benzaldehyde.

The starting substances of the formula (II) are known and/or can beprepared by processes known per se (compare EP-A 223,406; EP-A 249,708;JP-A 63258467 - cit. in Chem. Abstracts 110, 130532a; JP-A 63258463 -cit. in Chem. Abstracts 110, 192853q; EP-A 287,079).

The starting substances of the general formula (IIa) ##STR12## in whichA, Q, R¹, R² and R⁴ have the meanings given above, m represents thenumbers 1 or 2 and

R³⁻¹ represents fluorine and, if appropriate, additionally chlorine,

are new and subject-matter of the present application.

In formula (IIa), A, Q, R¹, R² and R⁴ preferably, or in particular, havethose meanings which have already been given above in connection withthe description of the compounds of the formula (I) according to theinvention as being preferred, or as particularly preferred, for A, Q,R¹, R² and R⁴ ; m preferably represents the numbers 1 or 2 and R³⁻¹preferably represents fluorine.

The new compounds of the formula (IIa) are obtained when halogencompounds of the general formula (IV) ##STR13## in which m, A, Q, R¹, R²and R³⁻¹ have the meaning given above in formula (IIa),

are treated with a metallating agent such as, for example, butyllithium,in the presence of an inert diluent such as, for example,tetrahydrofuran, at temperatures between -20° C. and -120° C.,preferably between -50° C. and -80° C., the product is subsequentlyreacted in situ with carboxamides of the general formula (V)

    R.sup.4 --CO--NR.sub.2                                     (V)

in which

R⁴ has the meaning given above and

R represents alkyl,

at temperatures between 0° C. and -80° C., and the product is worked upby customary methods (cf. the preparation examples).

In formula (IV), A, Q, R¹ and R² preferably, or in particular, havethose meanings which have already been given above in connection withthe description of the compounds of the formula (I) according to theinvention as being preferred, or as particularly preferred, for A, Q, R¹and ² R; m preferably represents the numbers 1 or 2 and R³⁻¹ preferablyrepresents fluorine.

The halogen compounds of the formula (IV) were hitherto not known fromthe literature and are likewise subject-matter of the presentapplication.

The new compounds of the formula (IV) are obtained when halogenated(thio)phenols of the formula (VI) ##STR14## in which m, Q and R³⁻¹ havethe meaningsgiven above,

are reacted with reactive azines of the formula (VII) ##STR15## in whichA, R¹ and R² have the meanings given above and

G represents a nucleofugic leaving group,

if appropriate in the presence of an acid acceptor such as potassiumcarbonate, and if appropriate in the presence of a diluent such as, forexample, acetonitrile, at temperatures between 20° C. and 120° C. (cf.the preparation examples).

In formula (VI), m preferably represents the numbers 1 or 2, Qpreferably represents oxygen and R³⁻¹ preferably represents fluorine.

The halogenated (thio)phenols of the formula (VI) are known chemicalsfor synthesis.

In formula (VII), A, R¹ and R² preferably, or in particular, have thosemeanings which have already been given above in connection with thedescription of the compounds of the formula (I) according to theinvention as being preferred, or as particularly preferred, for A, R¹and R² ; G preferably represents chlorine or methylsulphonyl.

The reactive azines of the formula (VII) are known and/or can beprepared by processes known per se (cf. J. Chem. Soc. 1957, 1830, 1833;J. Org. Chem. 26 (1961), 792; U.S. Pat. No. 3,308,119; U.S. Pat. No.4,711,959).

In formula (V), R⁴ preferably, or in particular, has those meaningswhich have already been given above in connection with the descriptionof the compounds of the formula (I) according to the invention as beingpreferred, or as particularly preferred, for R⁴ ; R preferablyrepresents C₁ -C₄ -alkyl, in particular methyl.

The carboxamides of the formula (V) are known chemicals for synthesis.

Formula (III) provides a general definition of the amino or methylenecompounds furthermore to be used as starting substances in the processaccording to the invention for the preparation of compounds of theformula (I).

In formula (III), Z preferably, or in particular, has those meaningswhich have already been given above in connection with the descriptionof the compounds of the formula (I) according to the invention as beingpreferred, or as particularly preferred, for Z.

Examples of the starting substances of the formula (III) which may bementioned are: ammonia, hydroxylamine, hydrazine, methylamine,ethylamine, propylamine, isopropylamine, butylamine, isobutylamine,sec-butylamine, tert-butylamine, allylamine, propargylamine, O-methyl-,O-ethyl-, O-propyl-, O-isopropyl-, O-butyl-, O-isobutyl- andO-sec-butyl-hydroxylamine, O-allyl-hydroxylamine, methyl aminooxyacetateand ethyl aminooxyacetate, methyl α-aminooxy-propionate and ethylα-aminooxypropionate, methylhydrazine, ethylhydrazine, propylhydrazine,isopropylhydrazine, butylhydrazine, isobutylhydrazine,sec-butyl-hydrazine, tert-butylhydrazine, N,N-dimethylhydrazine,acetohydrazide, propionylhydrazide, methoxycarbonylhydrazine,ethoxycarbonylhydrazine, methylsulphonylhydrazine,ethylsulphonylhydrazine, phenylhydrazine, benzoylhydrazine,benzenesulphonyl hydrazide, p-toluenesulphonyl hydrazide, malonic acid,cyanoacetic acid, malononitrile, methyl cyanoacetate and ethylcyanoacetate, dimethyl malonate and diethyl malonate, andγ-butyrolactone.

The starting substances of the formula (III) are known chemicals forsynthesis.

The process according to the invention for the preparation of the newsubstituted azines of the formula (I) is preferably carried out usingdiluents. Suitable diluents besides water are virtually all inertorganic solvents. These preferably include aliphatic and aromatic,optionally halogenated hydrocarbons such as pentane, hexane, heptane,cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene,xylene, methylene chloride, ethylene chloride, chloroform, carbontetrachloride, chlorobenzene and o-dichlorobenzene, ethers such asdiethyl ether and dibutyl ether, glycol dimethyl ether and diglycoldimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone,methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone,esters such as methyl acetate and ethyl acetate, nitriles such as, forexample, acetonitrile and propionitrile, amides such as, for example,dimethylformamide, dimethylacetamide and N-methyl-pyrrolidone, and alsodimethyl sulphoxide, tetramethylene sulphone and hexamethylphosphorictriamide.

If appropriate, the process according to the invention is carried out inthe presence of a reaction auxiliary. Suitable reaction auxiliaries aresubstances which are customarily used for controlling and/oraccelerating condensation reactions between carbonyl compounds and aminoor methylene compounds. These include, in particular, nitrogen compoundssuch as, for example, ammonium acetate, β-alanine, pyridine andpiperidine.

In the process according to the invention, the reaction temperatures canbe varied within a substantial range. In general, the reaction iscarried out at temperatures between 0° C. and 150° C., preferably attemperatures between 10° C. and 120° C.

In general, the process according to the invention is carried out underatmospheric pressure. However, it is also possible to carry out theprocess under increased or reduced pressure.

For carrying out the process according to the invention, the startingsubstances required in each case are generally employed in approximatelyequimolar amounts. However, it is also possible to use one of the twocomponents employed in each case in a larger excess. In general, thereactions are carried out in a suitable diluent, if appropriate in thepresence of a reaction auxiliary, and the reaction mixture is stirredfor several hours at the particular temperature required. Working-up inthe process according to the invention is carried out in each case bycustomary methods (compare the preparation examples).

The active compounds according to the invention can be used asdefoliants, desiccants, agents for destroying broad-leaved plants and,in particular, as weed-killers. By weeds, in the broadest sense, thereare to be understood all plants which grow in locations where they areundesired. Whether the substances according to the invention act astotal or selective herbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum and Mercurialis.

Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotyledon cultures of the genera: Oryza, Zea, Triticum, Hordeum,Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus andAllium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration, for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, onlawns, turf and pasture lands and for the selective combating of weedsin annual cultures.

The compounds of the formula (I) according to the invention can beemployed both pre-emergence and post-emergence methods for combatingmonocotyledon and dicotyledon weeds.

To a certain extent, the compounds according to the invention also showa fungicidal action, for example against Pyricularia oryzae.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusting agents, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are prepared in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene, oralkylnaphthalenes, chlorinated aromatics and chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample petroleum fractions, mineral and vegetable oils, alcohols, suchas butanol or glycol as well as their ethers and esters, ketones, suchas acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates, assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,corn cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumin hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methyl-cellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic polymersin the form of powders, granules or latexes, such as gum arabic,polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

For combating weeds, the active compounds according to the invention, assuch or in their formulations, can also be used as mixtures with knownherbicides, finished formulations or tank mixes being possible.

Suitable herbicides for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dione(AMETHYDIONE) or N-(2-benzothiazolyl)-N,N,-dimethylurea(METABENZTHIAZURON) for combating weeds in cereals;4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one (METAMITRON) forcombating weeds in sugar beets and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one(METRIBUZIN) for combating weeds in soy beans; furthermore also2,4-dichlorophenoxyacetic acid (2,4-D); 4-(2,4-dichlorophenoxy)-butyricacid (2,4-DB); 2,4-dichlorophenoxy- propionic acid (2,4-DP);5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-benzoic acid(ACIFLUORFEN);2-chloro-2',6'-diethyl-N-methoxy-methylacetanilide(ALACHLOR);2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine(ATRAZINE); methyl2[[[[[(4,6-dimethoxypyrimidin-2-yl)-amino]-carbonyl]-amino]sulphonyl]-methyl]-benzoate(BENSULFURON);3-isopropyl-2,1,3-benzothiadiazin-4-one 2,2-dioxide (BENTAZONE); methyl5-(2,4-dichlorophenoxy)-2-nitrobenzoate(BIFENOX);3,5-dibromo-4-hydroxy-benzonitrile; (BROMOXYNIL); ethyl2-{[(4-chloro-6-methoxy-2-pyrimidinyl)-aminocarbonyl]-aminosulphonyl}-benzoate(CHLORIMURON); N,N-dimethyl-N'-(3-chloro-4-methylphenyl)-urea(CHLORTOLURON);2-chloro-4-ethylamino-6-(3-cyanopropylamino)-1,3,5-triazi (CYANAZINE);4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5(4H)-one (ETHIOZIN);2-{4-[(6-chloro-2-benzoxazolyl)oxy]-phenoxy}-propanoic acid, its methylester or its ethyl ester (FENOXAPROP);[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)-oxy]-acetic acid or its1-methylheptyl ester (FLUROXYPYR);5-(2-chloro-4-trifluoromethylphenoxy)-N-methylsulphonyl-2-nitrobenzamide(FOMESAFEN); N-phosphonomethyl-glycine (GLYPHOSATE);2-{4-[(3-chloro-5-(trifluoromethyl)-2-pyridinyl)-oxy]-phenoxy}-propanoicacid or its ethyl ester (HALOXYFOP); methyl2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4(5)-methylbenzoate(IMAZAMETHABENZ);2-[5-methyl-5-(1-methylethyl)-4-oxo-2-imidazolin-2-yl]-3-quinolinecarboxylicacid (IMAZAQUIN);2-[4,5-dihydro-4-methyl-4-isopropyl-5-oxo-(1H)-imidazol-2-yl]-5-ethyl-pyridine-3-carboxylicacid (IMAZETHAPYR); 3,5-diiodo-4-hydroxybenzonitrile (IOXYNIL);N,N-dimethyl-N'-(4 -isopropylphenyl)-urea (ISOPROTURON);(2-methyl-4-chlorophenoxy)-acetic acid (MCPA);(4-chloro-2-methylphenoxy)-propionic acid (MCPP);N-methyl-2-(1,3-benzothiazol-2-yloxy)-acetanilide (MEFENACET);2-ethyl-6-methyl-N-(1-methyl-2-methoxyethyl)-chloroacetanilide(METOLACHLOR);2-{[[((4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino)-carbonyl]-amino]-sulphonyl}-benzoicacid or its methyl ester (METSULFURON);N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitroaniline (PENDIMETHALIN);2-[1-(ethoxamino)-butylidene] -5-(2-ethylthiopropyl)-1,3-cyclohexadione(SETHOXYDIM); 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine(TERBUTRYNE); methyl3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)-amino]-carbonyl]-amino]-sulphonyl]-thiophene-2-carboxylate(THIAMETURON) and 2,6-dinitro-4-trifluoromethyl-N,N-dipropylaniline(TRIFLURALIN). Surprisingly, some mixtures also show a synergisticaction.

Mixtures with other known active compounds, such as fungicides,insecticides, acaricides, nematicides, bird repellents, plant nutrientsand agents which improve soil structure, are also possible.

The active compounds can be used as such, in the form of theirformulations or in the use forms prepared therefrom by further dilution,such as ready-to-use solutions, suspensions, emulsions, powders, pastesand granules. They are used in the customary manner, for example bywatering, spraying, atomizing or scattering.

The active compounds according to the invention can be applied eitherbefore or after emergence of the plants. They can also be incorporatedinto the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 0.01 and 10 kg of active compound perhectare of soil surface, preferably between 0.05 and 5 kg per ha.

The preparation and use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example 1 ##STR16##

A mixture of 2.7 g (10 mmol) of2-(4,6-dimethoxypyrimidin-2-yl-oxy)-benzaldehyde, 1.1 g (10 mmol)phenylhydrazine and 40 ml of toluene is stirred for 2 hours at 20° C.and subsequently concentrated. The residue is brought to crystallizationwith ethanol/water (1:1), and the crystallized product is isolated byfiltration with suction.

2.6 g (75% of theory) of2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-benzaldehyde phenylhydrazone ofmelting point are obtained.

Example 2 ##STR17##

A mixture of 2.6 g (10 mmol) of2-(4,6-dimethoxypyrimidin-2-yl-oxy)-benzaldehyde, 0.67 g (10 mmol)malononitrile, 0.1 g of ammonium acetate and 80 ml of toluene is heatedto the boil for 5 hours on a water separator. The mixture issubsequently concentrated, and the residue is brought to crystallizationwith diethyl ether/petroleum ether. The crystalline product is isolatedby filtration with suction.

2.2 g (71% of theory) ofα-(2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-phenyl)-methylene-malononitrileof melting point 123° C. are obtained.

Examples of other compounds of the formula (I) which can be preparedanalogously to Examples 1 or 2 and following the general description ofthe preparation process according to the invention or by subsequentreactions following customary methods are those listed in Table 1 below.##STR18## (Q is bonded always in the 2-position).

                                      TABLE 1                                     __________________________________________________________________________    Examples of the compounds of the formula (I)                                  Example No.                                                                          A   Q  R.sup.1                                                                           R.sup.2                                                                           R.sup.3                                                                              R.sup.4                                                                          m  Z                 Melting Point                                                                 (°C.)             __________________________________________________________________________           (2-Position)                                                           3      CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOC.sub.2 H.sub.5                                                                             70                      4      N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOH            196                      5      N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOC.sub.2 H.sub.5                                                                            128                      6      CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCH.sub.2 OH     (amorphous)              7      CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR19##        124                      8      CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR20##        147                      9      CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR21##        126                      10     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR22##        139                      11     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  C(COOC.sub.2 H.sub.5).sub.2                                                                     (amorphous)              12     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1  CHCOOH            193                      13     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCH.sub.2 OH     (amorphous)              14     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOCH(CH.sub.3).sub.2                                                                         (amorphous)              15     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)CF.sub.3                                                                         H  1  CHCOOH            (amorphous)              16     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR23##        131                      17     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR24##        182                      18     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR25##        153                      19     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR26##        (amorphous)              20     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR27##        (amorphous)              21     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR28##        (amorphous)              22     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (4-)F  H  1  CHCOOH            179                      23     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1  CHCH.sub.2 OH     (amorphous)              24     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (4-)F  H  1  CHCH.sub.2 OH     (amorphous)              25     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (4-)F  H  1  C(COOC.sub.2 H.sub.5).sub.2                                                                     (amorphous)              26     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCHO              94                      27     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)CH.sub.3                                                                         H  1  CHCOOH            162                      28     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl H  1  CHCOOH            200                      29     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl H  1  C(COOC.sub.2 H.sub.5).sub.2                                                                     (amorphous)              30     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl H  1  CHCH.sub.2 OH     (amorphous)              31     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)CH.sub.3                                                                         H  1  CHCH.sub.2 OH     (amorphous)              32     CH  O  CH.sub.3                                                                          OCH.sub.3                                                                         --     H  0  C(COOC.sub.2 H.sub.5).sub.2                                                                     (amorphous)              33     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR29##        (amorphous)              34     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR30##        123                      35     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR31##        (amorphous)              36     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR32##        (amorphous)              37     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR33##        (amorphous)              38     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR34##        (amorphous)              39     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCN              (amorphous)              40     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR35##        175                      41     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR36##         85                      42     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR37##        (amorphous)              43     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1  CHCN              (amorphous)              44     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CFCOOC.sub.2 H.sub.5                                                                            (amorphous)              45     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1  CFCOOC.sub.2 H.sub.5                                                                            (amorphous)              46     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR38##        (amorphous)              47     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR39##        (amorphous)              48     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR40##        (amorphous)              49     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR41##        (amorphous)              50     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR42##        (amorphous)              51     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR43##        104                      52     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR44##        102                      53     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR45##        (amorphous)              54     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR46##        (amorphous)              55     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR47##        238                      56     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR48##        141                      57     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR49##        (amorphous)              58     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR50##        119                      59     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR51##        (amorphous)              60     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR52##        191                      61     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR53##        200                      62     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  NNHSO.sub.2CH.sub.3                                                                             (amorphous)              63     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR54##        149                      64     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR55##        134                      65     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     CH.sub.3                                                                         0                                                                                 ##STR56##        116                      66     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR57##         82                      67     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CFCOOH            (amorphous)              68     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR58##        184                      69     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR59##        165                      70     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR60##        172                      71     CBr O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOH            220                      72     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR61##        (amorphous)              73     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR62##        143                      74     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOH            135                      75     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  CHCOOCH.sub.3     121                      76     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR63##        168                      77     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR64##        108                      78     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1  CHCOOH            163                      79     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR65##        176                      80     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR66##        157                      81     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR67##        116                      82     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR68##        170                      83     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR69##         82                      84     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR70##        (amorphous)              85     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR71##        158                      86     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR72##         98                      87     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR73##        (amorphous)              88     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR74##         73                      89     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR75##         82                      90     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR76##        186                      91     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR77##        184                      92     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR78##        153                      93     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR79##        203                      94     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl H  1                                                                                 ##STR80##        119                      95     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl H  1                                                                                 ##STR81##        134                      96     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR82##        179                      97     N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR83##        176                      98     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR84##        121                      99     CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR85##         97                      100    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR86##        172                      101    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR87##        103                      102    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR88##        119                      103    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR89##        123                      104    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR90##         94                      105    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR91##        102                      106    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR92##        142                      107    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR93##        179                      108    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR94##         99                      109    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR95##        168                      110    N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR96##        245                      111    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR97##        196                      112    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR98##         50                      113    N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR99##         60                      114    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR100##        68                      115    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR101##        54                      116    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR102##        54                      117    N   O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR103##       133                      118    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1                                                                                 ##STR104##        88                      119    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR105##        61                      120    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR106##       (amorphous)              121    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  NNHCOOC(CH.sub.3).sub.3                                                                         105                      122    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR107##       138                      123    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  NOCOOCH.sub.3      86                      124    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  NOCH.sub.2COOC.sub.2 H.sub.5                                                                    (amorphous)              125    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0                                                                                 ##STR108##       (amorphous)              126    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)CH.sub.3                                                                         H  1  C(CN).sub.2        72                      127    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)CH.sub.3                                                                         H  1                                                                                 ##STR109##        96                      128    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)CH.sub.3                                                                         H  1                                                                                 ##STR110##       (amorphous)              129    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1  NNH COOCH.sub.3   133                      130    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1  NNHCOOC(CH.sub.3).sub.3                                                                         (amorphous)              131    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl,(6-)F                                                                         H  2                                                                                 ##STR111##       152                      132    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)Cl,(6-)F                                                                         H  2                                                                                 ##STR112##       217                      133    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR113##       155                      134    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR114##       143                      135    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)Cl,(5-)F                                                                         H  2                                                                                 ##STR115##       189                      136    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5-)F  H  1  NNHCOOC(CH.sub.3).sub.3                                                                         (amorphous)              137    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR116##       160                      138    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR117##       170                      139    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR118##       164                      140    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR119##       216                      141    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR120##       138                      142    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR121##       147                      143    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR122##       181                      144    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR123##        93                      145    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR124##       168                      146    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR125##       222                      147    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR126##       170                      148    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR127##       82                       149    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2  NNHSO.sub.2 CH.sub.3                                                                            140                      150    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR128##       (amorphous)              151    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2  NNHCH.sub.3        75                      152    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR129##       (amorphous)              153    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)Cl                                                                             H  2                                                                                 ##STR130##       140                      154    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)Cl                                                                             H  2                                                                                 ##STR131##       230                      155    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         --     H  0  NNH.sub.2         (amorphous)              156    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (3,6-)F                                                                              H  2                                                                                 ##STR132##       172                      157    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (3,6-)F                                                                              H  2                                                                                 ##STR133##       191                      158    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (6-)F  H  1                                                                                 ##STR134##       196                      159    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR135##       215                      160    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR136##       198                      161    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR137##        90                      162    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR138##       108                      163    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR139##        89                      164    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR140##       156                      165    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR141##       204                      166    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR142##       227                      167    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR143##       185                      168    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR144##       171                      169    CH  O  OCH.sub.3                                                                         OCH.sub.3                                                                         (5,6-)F                                                                              H  2                                                                                 ##STR145##       114                      __________________________________________________________________________

For example, the compound listed in Table 1 as Example 72 can beprepared as follows: ##STR146## A mixture of6-fluoro-2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-benzaldehyde (1.0 g, 3.6mmol), phenylhydrazi (0.39 g, 3.6 mmol) and toluene (20 ml) is stirredfor 10 hours at 20° C. and subsequently concentrated.

0.8 g (60% of theory) of6-fluoro-2-(4,6-dimethoxypyrimidin-2-yl-oxy)-benzaldehydephenylhydrazone is obtained as an amorphous residue.

Starting substances of the formula (II) Example (II-1) ##STR147##

A mixture of 11.0 g (50 mmol) of4,6-dimethoxy-2-methylsulphonyl-pyrimidine, 6.1 g (50 mmol) of2-hydroxybenzaldehyde, 6.9 g of potassium carbonate and 170 ml ofacetonitrile is refluxed for 5 hours and subsequently concentrated. Theresidue is shaken with water/ethyl acetate, and the organic phase isseparated off, dried with sodium sulphate and filtered. The solvent iscarefully removed from the filtrate by distillation under a water pumpvacuum.

7.8 g (60% of theory) of2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-benzaldehyde are obtained as asolid residue of melting point 81° C.

Example (II-2) ##STR148##

6.0 g (25 mmol) of 2-(3-fluoro-phenoxy)-4,6-dimethoxypyrimidine areintroduced into 150 ml of tetrahydro the mixture is cooled to -78° C.,and 18 ml of a 15% strength solution of butyllithium in hexane areadded. After the reaction mixture has been stirred for one hour at -78°C., 2.2 g (30 mmol) of dimethylformamide are added dropwise, andstirring is continued for one hour without further external cooling. 50ml of a 5% strength aqueous solution of sodium dihydrogen phosphate anda further 200 ml of water are then added, and the solution is shakenthree times with 150 ml portions of diethyl ether. The combined organicphases are dried with sodium sulphate and filtered. The filtrate isconcentrated under a water pump vacuum, and the residue is purified bychromatography (methylene chloride/silica gel).

3.9 g (56% of theory) of2-(4,6-dimethoxy-pyrimidin-2-yl-oxy)-6-fluoro-benzaldehyde of meltingpoint obtained.

Other examples of the new compounds of the formula (IIa) which can beobtained analogously to Example (II-2) are the following:

Example (II-3) ##STR149##

Melting point: 114° C.

Example (II-4) ##STR150##

Melting point: 113° C.

Example (II-5) ##STR151## Example (II-6) ##STR152##

Melting point: 94° C.

Example (II-7) ##STR153##

Melting point: 125° C.

Starting substances of the formula (IV) Example (IV-1) ##STR154##

3-Fluorophenol (11.3 g, 100 mmol) and potassium carbonate (13.8 g) areadded to 4,5-dimethoxy-2-=methylsulphonylpyrimidine (21.8 g, 100 mmol)in acetonitrile (300 ml). The mixture is refluxed for 2 hours, pouredinto ice-water and extracted with diethyl ether. The extract is driedover sodium sulphate then concentrated.

In this manner, 21.4 g (91% of theory) of2-(3-fluorophenoxy)-4,6-dimethoxy-pyrimidine of melting point 45° C. areobtained.

Another example of a new compound of the formula (IV) which can beobtained analogously to Example (IV-1) is the following:

Example (IV-2) ##STR155##

Melting point: 85° C.

The biological activities of the novel compounds is shown in thefollowing examples illustrating their use.

Example A Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote: ##EQU1## In this test, a powerful action against weeds is shown,for example, by the compounds according to Preparation Examples (1),(2), (11), (23), (42), (50), (56), (57), (72), (73), (74), (76), (77),(78), (79), (80), (81), (82), (83), (84), (85), (86), (87), (88), (89),(92), (121), (122), (123), (124) and (135).

Example B Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amounts of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 1,000 1 of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote: ##EQU2## In this test, a powerful action against weedsis shown, for example, by the compounds according to PreparationExamples (1), (2), (7), (12), (42), (44), (50), (58), (59), (60), (61),(62), (63), (64), (65), (66), (67), (68), (69), (70), (72), (73), (74),(76), (77), (78), (79), (80), (81), (82), (83), (84), (85), (86), (87),(88), (89), (90), (91), (92), (93), (120), (121), (123), (124) and(125).

It Will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A substituted azine of the formula, in which ##STR156## mrepresents the numbers 0, 1, or 2, A represents a C-X group where Xrepresents hydrogen or halogen,Q represents oxygen or sulphur, R¹ and R²are identical or different and represent hydrogen, halogen, C₁ -C₄-alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₂ -alkoxy-C₁ -C₂ -alkyl, C₁ -C₄-alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylaminoor di-(C₁ -C₂ -alkyl)-amino, R³ represents amino, hydroxyl, halogen, C₁-C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₄-halogenoalkoxy, C₁ -C₄ -alkylamino, di-(C₁ -C₂ -alkyl)-amino, C₁ -C₄-alkyl-carbonylamino,C₁ -C₄ -alkoxy-carbonylamino or C₁ -C₄-alkylsulphonylamino, R⁴ represents hydrogen or C₁ -C₄ -alkyl and ZrepresentsN-R⁵ or ##STR157## where R⁵ represents hydrogen, amino orrepresents C₁ -C₆ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, carboxy-C₁-C₂ -alkoxy, C₁ -C₆ -alkoxycarbonyloxy, C₁ -C₄ -alkoxycarbonyl-C₁ -C₂-alkoxy, C₁ -C₆ -alkylamino, di-(C₁ -C₂ -alkyl)-amino, C₁ -C₆-alkyl-carbonylamino, C₁ -C₆ -alkoxy-carbonylamino or C₁ -C₆-alkyl-sulphonylamino, each of which is optionally substituted byhalogen, or represents phenyl, phenyl-C₁ -C₄ -alkyl,phenylaminocarbonyloxy, phenylamino, phenyl-C₁ -C₄ -alkylamino, N-(C₁-C₄ -alkyl)-phenylamino, pyridylamino, pyrimidylamino,pyridylcarbonylamino, phenylcarbonylamino, furylcarbonylamino,thienylcarbonylamino or phenylsulphonylamino, each of which isoptionally substituted by nitro, hydroxyl, amino, cyano, carboxyl,halogen, C₁ -C₄ -alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₂-halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₂ -halogenoalkylthio, C₁ -C₄-alkoxycarbonyl and/or di-(C₁ -C₂ -alkyl)-amino, R⁶ represents hydrogen,halogen, cyano, carboxyl, C₁ -C₆ -alkoxy-carbonyl, C₁ -C₆-alkylcarbonylamino or di-(C₁ -C₄ -alkoxy)-phosphoryl, and R⁷ representsformyl, cyano, carboxyl, hydroxymethyl or carbamoyl, or represents C₁-C₆ -alkoxy-carbonyl, C₅ -C₆ -cycloalkyloxy-carbonyl, C₁ -C₆-alkylthiocarbonyl, C₁ -C₆ -alkylamino-carbon-yl or C₅ -C₆-cycloalkylamino-carbonyl, each of which is optionally substituted byhalogen, carboxyl or C₁ -C₄ -alkoxy-carbonyl, or represents di-(C₁ -C₂-alkyl)-aminocarbonyl, or C₁ -C₄ -alkylamino-carbonyl-C₁ -C₄-alkoxy-carbonyl, or di-(C₁ -C₂ -alkyl)-aminocarbonyl-C₁ -C₄-alkoxy-carbonyl, or phenylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, orN-methylphenylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, or representspyrrolidinylcarbonyl, piperidinylcarbonyl, morpholinylcarbonyl orpiperazinylcarbonyl, each of which is optionally substituted by methyland/or ethyl, or represents phenoxycarbonyl, phenyl-C₁ -C₄-alkoxycarbonyl, furylmethoxycarbonyl, thienylmethoxycarbonyl,phenylthiocarbonyl, phenyl-C₁ -C₄ -alkylthio-carbonyl,phenylaminocarbonyl, phenyl-C₁ -C₄ -alkylamino-carbonyl, N-(C₁ -C₄-alkyl)phenylamino-carbonyl or phenylhydrazinocarbonyl, each of which isoptionally substituted by nitro, amino, cyano, carboxyl, halogen, C₁ -C₄-alkyl, C₁ -C₂ -halogenoalkyl, C₁ -C₄ -alkoxy, C₁ -C₂ -halogenoalkoxy,C₁ -C₄ -alkylthio, C₁ -C₂ -halogenoalkylthio, C₁ -C₄ -alkoxycarbonyland/or di-(C₁ -C₂ -alkyl)-amino, or represents the groupphthalimidoxycarbonyl, or represents the group ##STR158## or togetherwith R⁶ represents the group --CO--O--(CH₂)_(n) -- where n representsthe numbers 2 or
 3. 2. A substituted azine according to claim 1, inwhichm represents the numbers 0, 1, or 2, A represents a CH group, Qrepresents oxygen, R¹ represents hydrogen, chlorine, methyl, ethyl,trifluoromethyl, methoxymethyl, methoxy, ethoxy, difluoromethoxy,methylthio, methylamino, ethylamino or dimethylamino, R² representshydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,difluoromethoxy, methylthio, methylamino, ethylamino or dimethylamino,R³ represents maino, hydroxyl, fluorine, chlorine, bromine, methyl,ethyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy,methylamino, dimethylamino, acetylamino, methoxycarbonylamino ormethylsulphonylamino, R⁴ represents hydrogen or methyl and ZrepresentsN-R⁵ or ##STR159## where R⁵ represents hydrogen, amino, ormethyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, alyl, propargyl, carboxymethoxy, carboxyethoxy,methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy,butoxycarbonyloxy, methoxycarbonylmethoxy, ethoxycarbonylmethoxy,methoxycarbonylethoxy, ethoxycarbonylethoxy, methylamino, ethylamino,propylamino, isopropylamino, butylamino, isobutylamino, secbutylamino,tert-butylamino, dimethylamino, acetylamino, propionylamino,methoxycarbonylamino, ethoxycarbonylamino, methylsulphonylamino orethylsulphonylamino or represents phenyl, benzyl,phenylaminocarbonyloxy, phenylamino, benzylamino, N-methyl-phenylamino,pyridylamino, pyrimidylamino, pyridylcarbonylamino, phenylcarbonylamino,furylcarbonylamino, thienylcarbonylamino or phenylsulphonylamino, eachof which is optionally substituted by nitro, hydroxy, cyano, fluorine,chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy,methylthio or trifluoromethylthio, R⁶ represents hydrogen, fluorine,chlorine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄-alkylcarbonylamino, dimethoxyphosphoryl or diethoxyphosphoryl, and R⁷represents formyl, cyano, carboxyl, hydroxymethyl or carbamoyl, orrepresents C₁ -C₄ -alkoxy-carbonyl, C₅ -C₆ -cycloalkyloxy-carbonyl, C₁-C₄ -alkylthiocarbonyl, C₁ -C₄ -alkylamino-carbonyl or C₅ -C₆-cycloalkylamino-carbonyl, each of which is optionally substituted byfluorine, chlorine, carboxyl or C₁ -C₄ -alkoxy-carbonyl, or representsdimethylaminocarbonyl, or C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄-alkoxy-carbonyl, or dimethylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, orN-methylphenylaminocarbonyl-C₁ -C₄ -alkoxy-carbonyl, or representspyrrolidinyl-carbonyl, piperidinylcarbonyl, morpholinyl-carbonyl orpiperazinylcarbonyl, each of which is optionally substituted by methyland/or ethyl, or represents phenoxycarbonyl, benzyloxycarbonyl,phenylthiocarbonyl, benzylthiocarbonyl, phenylaminocarbonyl,benzylaminocarbonyl, N-methyl-phenylaminocarbonyl orphenylhydrazinocarbonyl, each of which is optionally substituted bynitro, cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl,methoxy, trifluoromethoxy, methylthio or trifluoromethylthio, orrepresents phthalimidoxycarbonyl, or represents the group ##STR160## ortogether with R⁵ represents the group --CO--O--CH₂ CH₂ --.
 3. Asubstituted azine according to claim 2, in whichA represents a CH group,R¹ represents methoxy, R² represents methoxy, R³ represents fluorine,chlorine or methyl, and R⁴ represents hydrogen.
 4. A compound accordingto claim 1, wherein such compound isα-(2-(4,6-dimethoxy-pyridimin-2-yl-oxy)-6-fluoro-phenyl)-methylene-malononitrileof the formula ##STR161##
 5. A herbicidal composition comprising aherbicidally effective amount of a compound according to claim 1 and adiluent.
 6. A method of combating unwanted vegetation which comprisesapplying to such vegetation or to a locus from which it is desired toexclude such vegetation a herbicidally effective amount of a compoundaccording to claim
 1. 7. The method according to claim 6, wherein suchcompoundisα-(2-(4,6-dimethoxy-pyridimin-2-yl-oxy)-6-fluorophenyl)-methylene-malononitrile.8. A halogen compound of the formula ##STR162## in which A represents aC-X group where X represents hydrogen or halogen,Q represents oxygen orsulphur, R¹ and R² are identical or different and represent hydrogen,halogen, C₁ -C₄ -alkyl, C₁ -C₄ -halogenoalkyl, C₁ -C₂ -alkoxy-C₁ -C₂-alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁-C₄ -alkylamino or di-(C₁ -C₂ -alkyl)-amino, m represents the numbers 0or 1 and R³⁻¹ represents fluorine or chlorine.